Chemical and electronic interactions between CdSe nanocrystal quantum dots (NQDs) and Ru-polypyridine complexes are studied in solution. It is shown that photoluminescence (PL) can be used to effectively monitor the formation of NQD-complex assemblies in real time. It is also shown that with the aid of Langmuir isotherm modeling, the PL studies can be used to quantitatively characterize the composition of the assemblies and the strength of electronic interactions between their components. The approach demonstrated here is general and can be applied to other systems that combine semiconductor NQDs and appropriately functionalized organometallic or organic molecules interacting with NQDs via energy transfer, charge transfer, or other mechanisms leading to quenching of NQD emission.